Pretreatment of textile for inkjet printing

ABSTRACT

This invention pertains to inkjet printing on textile including using a pretreatment solution containing poly(acrylic) acid, hydrophilic copolymers of poly(acrylic) acid or mixtures thereof to control bleed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. No. 61/700531, filed Sep. 13, 2012, whichis incorporated by reference in its entirety.

BACKGROUND OF THE DISCLOSURE

This invention pertains to inkjet printing on a pretreated fabric withpigmented inkjet inks, and to a pretreatment solution for the fabricthat allows high quality printing thereon.

Digital printing methods such as inkjet printing are becomingincreasingly important for the printing of textiles and offer a numberof potential benefits over conventional printing methods such as screenprinting. Digital printing eliminates the set up expense associated withscreen preparation and can potentially enable cost effective short runproduction. Inkjet printing furthermore allows visual effects such astonal gradients and infinite pattern repeat sizes that cannot bepractically achieved with a screen printing process.

Bleed of one color into another is a typical problem in ink jet printingbecause inks have relatively low viscosity and tend to spread especiallyfor inkjet printers having capability of printing three or four primarycolors in a simultaneous (or near simultaneous) fashion. Such bleed ofone printing liquid into an adjacent printing liquid results inproduction of indistinct images with a poor degree of resolution.

Various methods have been proposed to prevent bleed of adjacent printingliquids. One method is to apply the two printing liquids at a distancefrom one another so that no intermingling or mixing of the printingliquids can occur. However, this method produces images of poorresolution. Another method involves a delay in applying the secondprinting liquid until the first printing liquid is completely dry. Thismethod is disadvantageous due to its inefficiencies. Yet anotherapproach to control bleed is to increase the rate of penetration of theprinting liquid into the substrate, but this causes a reduction ofoptical density.

U.S. Patent Application Publication No. 2007/0011819 discloses acomposition containing an ink receptor, a surfactant, a flame retardantand a fluorescent whitening agent to pretreat textiles.

U.S. Pat. No. 5,785,743 discloses the use of an organic acid componentin one ink to pair with another ink containing a pH sensitive colorantto reduce bleed for printing on paper.

A need exists for a textile pretreatment composition that canaccommodate all the various factors such as weave, weight and any otherapplied treatment from manufacturer that impact image quality. Thepresent disclosure satisfies this need by a providing a textilepretreatment composition to reduce bleed on natural and unnaturalfibers.

SUMMARY OF THE DISCLOSURE

An embodiment provides a method of digitally printing a textilecomprising the steps of:

-   -   (a) pretreating said textile with an aqueous pretreatment        solution comprising a bleed control agent selected from the        group consisting of poly(acrylic) acid, hydrophilic copolymers        of poly(acrylic) acid and mixtures thereof;    -   (b) drying the pretreated textile; and    -   (c) digitally printing the dried, pretreated textile with a        colored ink jet ink; wherein said bleed control agent is present        in an amount less than 5% by weight based on the weight of said        pretreatment solution, and said ink jet ink comprises a pigment,        a dispersant to disperse said pigment, and a polymeric binder,        and said binder is cross-linked with a cross-linking agent or        cross-linking groups present in said textile.

Another embodiment provides that the method optionally comprising anadditional post printing step of curing with melamine at a temperaturegreater than 180° C.

Another embodiment provides that the bleed control agent has a pH ofbetween 2 and 5.

Another embodiment provides that the textile is a synthetic material.

Another embodiment provides that the cross-linking agent is an epoxide.

Another embodiment provides that the pretreatment solution furthercomprises a surfactant.

Another embodiment provides that the pretreatment solution has aviscosity of less than 4 cPs.

Another embodiment provides that the polymeric binder is a polyurethane.

Yet another embodiment provides that the cross-linking agent is acarbodiimide.

These and other features and advantages of the present embodiments willbe more readily understood by those of ordinary skill in the art from areading of the following Detailed Description. Certain features of thedisclosed embodiments which are, for clarity, described above and belowas separate embodiments, may also be provided in combination in a singleembodiment. Conversely, various features of the disclosed embodimentsthat are described in the context of a single embodiment, may also beprovided separately or in any subcombination.

DETAILED DESCRIPTION

Unless otherwise stated or defined, all technical and scientific termsused herein have commonly understood meanings by one of ordinary skillin the art to which this disclosure pertains.

Unless stated otherwise, all percentages, parts, ratios, etc., are byweight.

When an amount, concentration, or other value or parameter is given aseither a range, preferred range or a list of upper preferable values andlower preferable values, this is to be understood as specificallydisclosing all ranges formed from any pair of any upper range limit orpreferred value and any lower range limit or preferred value, regardlessof whether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range.

When the term “about” is used in describing a value or an end-point of arange, the disclosure should be understood to include the specific valueor end-point referred to.

As used, herein, the term “dispersion” means a two phase system whereinone phase consists of finely divided particles (often in a colloidalsize range) distributed throughout a bulk substance, the particles beingthe dispersed or internal phase and the bulk substance being thecontinuous or external phase.

As used herein, the term “dispersant” means a surface active agent addedto a suspending medium to promote uniform and maximum separation ofextremely fine solid particles often of colloidal sizes. For pigments,the dispersants are most often polymeric dispersants, and thedispersants and pigments are usually combined, using a dispersingequipment.

As used herein, the term “OD” means optical density.

As used herein, the term “aqueous vehicle” refers to water or a mixtureof water and at least one water-soluble, or partially water-soluble(i.e., methyl ethyl ketone), organic solvent (co-solvent).

As used herein, the term “substantially” means being of considerabledegree, almost all.

As used herein, the term “dyne/cm” means dyne per centimeter, a surfacetension Unit.

As used herein, the term “cP” means centipoise, a viscosity unit.

As used herein, the term “mPa·s” means millipascal second, a viscosityunit.

As used herein, the term “mN·m⁻¹” means milliNewtons per meter, asurface tension unit.

As used herein, the term “mS·cm⁻¹” means milliSiemens per centimeter, aconductivity unit.

As used herein, the term “EDTA” means ethylenediaminetetraacetic acid.

As used herein, the term “IDA” means iminodiacetic acid.

As used herein, the term “EDDHA” meansethylenediamine-di(o-hydroxyphenylacetic acid).

As used herein, the term “DHEG” means dihydroxyethylglycine.

As used herein, the term “DTPA” meansdiethylenetriamine-N,N,N′,N″,N″-pentaacetic acid.

As used herein, the term “GEDTA” meansglycoletherdiamine-N,N,N′,N′-tetraacetic acid.

As used herein, Surfynol® 465 is a surfactant from Air Products(Allentown, Pa., U.S.A.).

As used herein, the term “RMSD” refers to root mean square deviation.

As used herein, the term “jettability” means good jetting propertieswith no clogging or deflection during printing.

As used herein, the term “DTG” means direct to garment.

Unless otherwise noted, the above chemicals were obtained from Aldrich(Milwaukee, Wis., U.S.A.) or other similar suppliers of laboratorychemicals.

The materials, methods, and examples herein are illustrative only exceptas explicitly stated, and are not intended to be limiting.

Pretreatment Solution

The pretreatment solution used in the method of the present disclosurecontains a bleed control agent selected from the group consisting ofpoly(acrylic) acid, hydrophilic copolymers of poly(acrylic) acid andmixtures thereof. Typically, the pretreatment solution comprises asolution of a poly(acrylic) acid, hydrophilic copolymers ofpoly(acrylic) acid or mixtures of poly(acrylic) acid, hydrophiliccopolymers of poly(acrylic) acid in water. Other organic ingredientssuch as co-solvents, swelling agents, coalescing agents, viscositymodifiers, typically, will not be included in the pretreatment solution.Optionally, the pretreatment solution contains a surfactant.Co-solvent(s) may be present when a surfactant is employed. Ingredientpercentages of the bleed control agent and the surfactant herein areweight percent based on the total weight of the pretreatment solution,unless otherwise indicated.

The bleed control agent is included in the pretreatment solution in aneffective amount to control bleed relative to without the bleed controlagent. Typically, the bleed control agent is present in the pretreatmentsolution at a level of at least about 0.2 by weight based on the totalweight of the pretreatment solution. The upper level is not limited, butis dictated by considerations such as compatibility with other inkcomponents. In one embodiment, the bleed control agent is present in arange of 0.1% to 5 based on the total weight of the pretreatmentsolution. In another embodiment, the bleed control agent is present in arange of 0.2% to 4% based on the total weight of the pretreatmentsolution. The appropriate levels of bleed control agent can be readilydetermined by one of ordinary skill in the art through routineexperimentation.

Surfactant

The surfactant can be any surfactant that lowers the surface tension ofthe multivalent salt solution to about 15 to about 10 dynes/cm orpreferably about 18 to about 30 dynes/cm. The amount of surfactant isfrom about 0.05% to about 10% by weight, typically from about 0.25 toabout 8% by weight and more typically from 0.5 to 6% by weight based onthe as received weight from the commercial supplier. Typically thesurfactant may contain some organic solvent components and/or water.

Up to 5% by weight of organic solvents may be included in thepretreatment solution especially those solvents that are part of theavailable surfactant.

Textile

The textile to be pretreated can be any textile suitable for printingwith colored inkjet inks. Typically, the textile includes naturalmaterial such as cotton and cotton blends, and synthetic material suchas polyester.

Pretreatment of Textile

Application of the pretreatment to the textile can be any convenientmethod and such methods are generally well-known in the art. One exampleis an application method referred to as padding. In padding, a textileis dipped in the pretreatment solution, then the saturated textile ispassed through nip rollers that squeeze out the excess solution. Theamount of solution retained in the textile can be regulated by the nippressure applied by the rollers. Other pretreatment techniques includespray application wherein the solution is applied by spraying on theface or face and back of the textile. Spraying can be limited to thedigitally printed area of the printed textile. An example of where thislimited spraying would be particularly applicable is in the digitalprinting of an image on preformed textile articles such as, for example,a T-shirts, caps, undergarments and like clothing articles.

After application of pretreatment, the textile may be dried in anyconvenient manner. The textile is preferably substantially dry at thetime of printing, such that the final percent moisture is(approximately) equal to the equilibrium moisture of the pretreatedtextile at ambient temperature. The absolute amount of moisture in thetextile, of course, can vary somewhat depending on the relative humidityof the surrounding air.

Colored Inkjet Inks

The colorant used for printing the colored image may be a dye or apigment. Dyes include disperse dyes, reactive dyes, acid dyes and thelike. The colored inkjet inks are preferably aqueous and do not containcomponents that are UV curable.

Pigmented inks are preferred. Pigmented inkjet inks suitable for use inthe present method typically comprise a pigment dispersed in a vehicle.Typically, the vehicle is an aqueous vehicle. More typically, thepigment ink comprises an anionically stabilized pigment dispersed in anaqueous vehicle.

The selected pigment(s) may be used in dry or wet form. For example,pigments are usually manufactured in aqueous media, and the resultingpigments are obtained as a water-wet presscake. In presscake form, thepigment does not agglomerate to the extent it would in dry form. Thus,pigments in water-wet presscake form do not require as much mixingenergy to de-agglomerate in the premix process as pigments in dry form.Representative commercial dry pigments are listed in U.S. Pat. No.5,085,698.

Some examples of pigments with coloristic properties useful in inkjetinks include: cyan pigments from Pigment Blue 15:3 and Pigment Blue15:4; magenta pigments from Pigment Red 122 and Pigment Red 202; yellowpigments from Pigment Yellow 14, Pigment Yellow 95, Pigment Yellow 110,Pigment Yellow 114, Pigment Yellow 128 and Pigment Yellow 155; redpigments from Pigment Orange 5, Pigment Orange 34, Pigment Orange 43,Pigment Orange 62, Pigment Red 17, Pigment Red 49:2, Pigment Red 112,Pigment Red 149, Pigment Red 177, Pigment Red 178, Pigment Red 188,Pigment Red 255 and Pigment Red 264; green pigments from Pigment Green1, Pigment Green 2, Pigment Green 7 and Pigment Green 36; blue pigmentsfrom Pigment Blue 60, Pigment Violet 3, Pigment Violet 19, PigmentViolet 23, Pigment Violet 32, Pigment Violet 36 and Pigment Violet 38;white pigments such as TiO₂ and ZnO; and black pigment carbon black. Thepigment names and abbreviations used herein are the “C.I.” designationfor pigments established by Society of Dyers and Colourists, Bradford,Yorkshire, UK and published in The Color Index, Third Edition, 1971.

The range of useful particle size after dispersion is typically fromabout 0.005 micrometers to about 15 micrometers. Typically, the pigmentparticle size should range from about 0.005 micrometers to about 5micrometers; and, specifically, from about 0.005 micrometers to about 1micrometers. The average particle size as measured by dynamic lightscattering is less than about 500 nm, typically less than about 300 nm.

The amount of pigment present in the ink is typically in the range offrom about 0.1% to about 25% by weight, and more typically in the rangeof from about 0.5% to about 10% by weight, based on the total weight ofink. If an inorganic pigment is selected, the ink will tend to containhigher percentages by weight of pigment than with comparable inksemploying organic pigment, since inorganic pigments generally havehigher densities than organic pigments.

Aqueous Vehicle

Selection of a suitable aqueous vehicle mixture depends on requirementsof the specific application, such as the desired surface tension andviscosity, the selected colorant, drying time of the ink, and the typeof substrate onto which the ink will be printed. Representative examplesof water-soluble organic solvents which may be utilized in the presentdisclosure are those that are disclosed in U.S. Pat. No. 5,085,698.

If a mixture of water and a water-soluble solvent is used, the aqueousvehicle typically will contain about 30% to about 95 of water with theremaining balance (i.e., about 70% to about 5%) being the water-solublesolvent. Compositions of the present disclosure may contain about 60% toabout 95% water, based on the total weight of the aqueous vehicle.

The amount of aqueous vehicle in the ink is typically in the range ofabout 70% to about 99.8%; specifically about 80% to about 99.8%, basedon total weight of the ink.

The aqueous vehicle can be made to be fast penetrating (rapid drying) byincluding surfactants or penetrating agents such as glycol ether(s) or1,2-alkanediols. Suitable surfactants include ethoxylated acetylenediols (e.g., Surfynols® series from Air Products), ethoxylated primary(e.g., Neodol® series from Shell) and secondary (e.g., Tergitol® seriesfrom Union Carbide) alcohols, sulfosuccinates (e.g., Aerosol® seriesfrom Cytec), organosilicones (e.g., Silwet® series from Witco) andfluoro surfactants (e.g., Zonyl® series from DuPont).

The amount of glycol ether(s) or 1,2-alkanediol(s) added must beproperly determined, but is typically in a range of from about 1% toabout 15% by weight, and more typically about 2% to about 10% by weight,based on the total weight of the ink. Surfactants may be used, typicallyin an amount of from about 0.01% to about 5%, and specifically fromabout 0.2% to about 2%, based on the total weight of the ink.

Polymeric Dispersant

The polymeric dispersant for the non-self-dispersing pigment(s) may be arandom or a structured polymer. Typically, the polymer dispersant is acopolymer of hydrophobic and hydrophilic monomers. The “random polymer”means polymers where molecules of each monomer are randomly arranged inthe polymer backbone. For a reference on suitable random polymericdispersants, see: U.S. Pat. No. 4,597,794. The “structured polymer”means polymers having a block, branched, graft or star structure.Examples of structured polymers include AB or BAB block copolymers suchas the ones disclosed in U.S. Pat. No. 5,085,698; ABC block copolymerssuch as the ones disclosed in EP Patent Specification No. 0556649; andgraft polymers such as the ones disclosed in U.S. Pat. No. 5,231,131.Other polymeric dispersants that can be used are described, for example,in U.S. Pat. No. 6,117,921, U.S. Pat. No. 6,262,152, U.S. Pat. No.6,306,994 and U.S. Pat. No. 6,433,117.

Polymeric Binders

Polymeric binders are polymers that improve the durability of a pigmentdispersion once it is deposited onto a surface. Unlike a dispersant,binder usually do not have the functionality or structure to adequatelystabilize a pigment dispersion. Binders often are added after a pigmentdispersion has been made.

The binders can be soluble in the vehicle or in a dispersed form, andcan be ionic or nonionic. Soluble binders include linear homopolymersand copolymers or block polymers. They also can be structured polymersincluding graft or branched polymers, stars and dendrimers. Thedispersed polymers may include, for example, latexes and hydrosols. Thepolymers may be made by any known process including, but not limited to,free radical, group transfer, ionic, condensation and other types ofpolymerization. They may be made by a solution, emulsion, or suspensionpolymerization process. Typical classes of polymeric binders includeanionic acrylic, styrene-acrylic and polyurethane polymer.

A polymeric binder is typically present at a level between about 0.01%and about 10% by weight, based on the total weight of an ink. The upperlimit is dictated by ink viscosity or other physical limitations.

Cross-linking of Polymeric Binder

The polymeric binder can contain cross-linkable functional moieties.Such polymeric binder is thus capable of reacting with a cross-linkingagent. Identified in the table below are suitable cross-linkablefunctional groups that are in the polymeric binder and the companioncross-linking groups that may be present in the cross-linking agent.

Cross-linkable Moieties Cross-linking Groups COOH Epoxide, Carbodiimide,Oxazoline, N-Methyol Hydroxyl Epoxide, Silane, Isocyanate, N-MethyolAmino Epoxide, Carbodiimide, Oxazoline, N-Methyol

The mole ratio of the cross-linkable moieties on the polymericdispersant to the cross-linking group(s) on the cross-linking agent isfrom 15:1 to 1:1.5, typically from 9:1 to 1:1.1, and most typically from8:1 to 1:1. In calculating the mole ratio, all cross-linkable moietieson the polymeric dispersants and all cross-linking groups on thecross-linking agent are included.

Alternatively, cross-linkable functional moieties on a polymeric bindercan react with cross-linking groups present in a textile resulting incross-linking.

Other Additives

Other ingredients, additives, may be formulated into the inkjet ink, tothe extent that such other ingredients do not interfere with thestability and jettability of the inkjet ink. This may be readilydetermined by routine experimentation by one skilled in the art.

Surfactants are commonly added to inks to adjust surface tension andwetting properties. Suitable surfactants include the ones disclosed inthe Vehicle section above. Surfactants are typically used in amounts upto about 5% and more typically in amounts up to 2% by weight, based onthe total weight of the ink.

Inclusion of sequestering (or chelating) agents such asethylenediaminetetraacetic acid (EDTA), iminiodiacetic acid (IDA),ethylenediamine-di(o-hydroxyphenylacetic acid) (EDDHA), nitrilotriaceticacid (NTA), dihydroxyethylglycine (DHEG),trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA),diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid (DTPA), andglycoletherdiamine-N,N,N′,N′-tetraacetic acid (GEDTA), and saltsthereof, may be advantageous, for example, to eliminate deleteriouseffects of heavy metal impurities.

Ink Sets

The term “ink set” refers to all the individual inks or other fluids aninkjet printer is equipped to jet. Ink sets typically comprise at leastthree differently colored inks. For example, a cyan (C), magenta (M) andyellow (Y) ink forms a CMY ink set. More typically, an ink set includesat least four differently colored inks, for example, by adding a black(K) ink to the CMY ink set to form a CMYK ink set. The magenta, yellowand cyan inks of the ink set are typically aqueous inks, and may containdyes, pigments or combinations thereof as the colorant. Such other inksare, in a general sense, well known to those of ordinary skill in theart.

In addition to the typical CMYK inks, an ink set may further compriseone or more “gamut-expanding” inks, including differently colored inkssuch as an orange ink, a green ink, a red ink and/or a blue ink, andcombinations of full strength and light strength inks such as light cyanand light magenta. Such other inks are, in a general sense, known to oneskilled in the art.

A typical ink set comprises a magenta, yellow, cyan and black ink,wherein the black ink is an ink according to the present disclosurecomprising an aqueous vehicle and a self-dispersing carbon blackpigment. Specifically, the colorant in each of the magenta, yellow andcyan inks is a dye.

Ink Properties

Jet velocity, separation length of the droplets, drop size and streamstability are greatly affected by the surface tension and the viscosityof the ink. Pigmented ink jet inks typically have a surface tension inthe range of about 20 dyne/cm to about 70 dyne/cm at 25° C. Viscositycan be as high as 30 cP at 25° C., but is typically somewhat lower. Theink has physical properties compatible with a wide range of ejectingconditions, i.e., driving frequency of the piezo element or ejectionconditions for a thermal head for either a drop-on-demand device or acontinuous device, and the shape and size of the nozzle. The inks shouldhave excellent storage stability for long periods so as not to clog to asignificant extent in an ink jet apparatus. Furthermore, the ink shouldnot corrode parts of the ink jet printing device it comes in contactwith, and it should be essentially odorless and non-toxic.

Although not restricted to any particular viscosity range or printhead,the inventive ink set is particularly suited to lower viscosityapplications such as those required by thermal printheads. Thus theviscosity of the inventive inks at 25° C. can be less than about 7 cP,typically less than about 5 cP, and more typically than about 3.5 cP.Thermal inkjet actuators rely on instantaneous heating/bubble formationto eject ink drops and this mechanism of drop formation generallyrequires inks of lower viscosity.

Printing Method

The present method relates to digitally printing a pretreated textile,where the pretreated textile may have been dried. Typically, thisinvolves the following steps:

-   -   (1) providing an inkjet printer that is responsive to digital        data signals;    -   (2) loading the printer with a textile to be printed, in this        case the pretreated textile;    -   (3) loading the printer with the above-mentioned inks or inkjet        ink sets; and    -   (4) printing onto the media using the inkjet ink or inkjet ink        set in response to the digital data signals.

After the printing the printed media may be heated to dry the printedimage. The heating conditions depend on the media and its maximumtemperature before melting, sagging or the like. A mild heatingcondition can be about 70° C. for about 15 minutes. A simple oven may beused for this post printing step.

Printing can be accomplished by any inkjet printer equipped for handlingand printing on textile. Commercial printers include, for example, theDupont™ Artistri™ 3210 and 2020 printers (Wilmington Del.), the MimakiTX (Nagano, Japan) series of printers, US Screen Printing T-ShirtPrinter (Tempe, Ariz.) and a DTG printer from Impression Technology(Sydney, Australia).

As indicated above, a variety of inks and ink sets are available for usewith these printers. Commercially available ink sets include, forexample, DuPont™ Artistri™ P3500 and P5000 series inks.

The amount of ink laid down on the textile can vary by printer model, byprint mode (resolution) within a given printer and by the percentcoverage need to achieve a given color. The preferred amount of ink ineach drop is less than about 35 picoliters, preferably less than about25 picoliters, and more preferably less than 15 picoliters. The amountof ink jetted that can be jetted onto a media is dependent on the mediaand the printer. For instance, for the DTG printer and transparencies adrop size of less than 10 picoliters produces the best printed image.

The following examples illustrate the invention without, however, beinglimited Thereto.

EXAMPLES Printing Conditions

The examples described below were done using DTG printers Belquette Mod1 and Flexijet. Printing was done with print resolution set to 1440×720dpi and 720×720 dpi. The textiles substrate used were Gildan 50/50polycotton blend shirts and 100% Augusta polyester shirt.

Pretreatment Solutions

Reagent grade poly(acrylic) acid (Aldrich) was mixed with deionizedwater until the poly(acrylic) acid was completely dissolved in asolution. The surface tension was measured with a Kruss tensiometer witha platinum plate at ambient temperature.

Evaluation of Color Characteristics

The L*, a*, b*, C* and h parameters of a CIE L*a*b* color scale weremeasured for each printed textile with and without a pretreatment usinga X-Rite colorimeter, Model SP-64 from X-Rite Inc. The total colordifference, ΔE* was then calculated. Also measured was gamut volume ofselected textile print set.

Various black and color inks from the DuPont™ Artistri™ P5000+ serieswere used in the examples summarized in Table 1 without furthermodification. Each test was carried out in duplicate and the averagedresult was tabulated. Printing was done with print resolution set to1440×720 dpi. As shown in Table 1 below, printing conducted on textiles,Gildan 50/50 polycotton, treated with the pretreatment (PT) solution ofthe instant disclosure showed significant total color differences whencompared to printing conducted on textiles without the pretreatment.

TABLE 1 Gildan 50/50 Color measurements Examples polycotton L* a* b* C*h Delta E Ex. 1 P5000+ Black with 34.56 0.48 −1.03 1.14 294.91 7.23 PTControl Ex. 1 P5000+ Black w/o 27.39 0.97 −1.78 2.03 298.71 PT Ex. 2P5000+ Cyan with 55.09 −10.62 −38.93 40.35 254.74 2.80 PT Control Ex. 2P5000+ Cyan w/o 56.06 −9.19 −39.20 40.27 256.80 PT Ex. 3 P5000+ Magenta83.61 −4.61 80.52 80.65 93.28 8.64 with PT Control Ex. 3 P5000+ Magenta84.37 −3.14 88.87 88.93 92.04 w/o PT Ex. 4 P5000+ Yellow 51.89 54.86−8.83 55.57 350.86 10.16 with PT Control Ex. 4 P5000+ Yellow 45.65 58.27−1.58 58.30 358.45 w/o PT Ex. 5 P5000+ Process 52.77 42.97 −27.44 50.9832.56 9.16 Red with PT Control Ex. 5 P5000+ Process 46.49 49.52 28.6957.23 30.08 Red w/o PT Ex. 6 P5000+ Process 52.46 −38.22 22.59 44.39149.41 3.69 Green with PT Control Ex. 6 P5000+ Process 50.88 −34.9322.49 41.55 147.22 Green w/o PT Ex. 7 P5000+ Process 41.70 6.99 −36.4237.08 280.87 11.20 Blue with PT Control Ex. 7 P5000+ Process 31.23 9.83−33.58 34.99 286.31 Blue w/o PT

As shown in Table 2 below, similar results were obtained printing on adifferent textile, 100% Augusta polyester.

TABLE 2 100% Augusta Color measurements no pretreatment ExamplesPolyester L* a* b* C* H Delta E Ex. 8 P5000+ Black Poly with 32.59 0.870.97 1.30 47.89 6.00 PT Control Ex. 8 P5000+ Black Poly w/o 38.56 1.021.47 1.79 55.22 PT Ex. 9 P5000+ Cyan Poly with 47.78 −1.99 −43.76 43.80267.40 9.68 PT Control Ex. 9 P5000+ Cyan Poly w/o 54.25 −5.94 −37.7338.20 261.05 PT Ex. 10 P5000+ Magenta Poly 51.35 55.36 −7.29 55.84352.50 6.07 with PT Control Ex. P5000+ Magenta Poly 55.17 52.10 −10.6953.18 348.40 10 w/o PT Ex. 11 P5000+ Yellow Poly 88.41 −7.90 81.02 81.4195.57 6.47 with PT Control Ex. P5000+ Yellow Poly w/o 88.86 −8.65 74.6175.11 96.61 11 PT Ex. 12 P5000+ Red Poly with 52.84 44.04 24.12 50.2128.71 5.40 PT Control Ex. P5000+ Red Poly w/o 54.85 40.77 20.32 45.5526.49 12 PT Ex. 13 P5000+ Green Poly with 48.28 −21.40 7.43 22.65 160.867.86 PT Control Ex. P5000+ Green Poly w/o 50.86 −28.08 10.67 30.04159.19 13 PT Ex. 14 P5000+ Blue Poly with 40.36 10.08 −24.53 26.52292.34 348 PT Control Ex. P5000+ Blue Poly w/o 41.61 12.33 −26.87 29.57294.66 14 PT

What is claimed is:
 1. A method of digitally printing :textilecomprising the steps of: (a) pretreating said textile with an aqueouspretreatment solution comprising a bleed control agent selected from thegroup consisting of poly(acrylic) acid, hydrophilic copolymers ofpoly(acrylic) acid and mixtures thereof; (b) drying the pretreatedtextile; and (c) digitally printing the dried, pretreated textile with acolored ink jet ink; wherein said bleed control agent is present in anamount less than 5% by weight based on the weight of said pretreatmentsolution, and said ink jet ink comprises a pigment, a dispersant todisperse said pigment, and a polymeric binder, and said binder iscross-linked with a cross-linking agent or cross-linking groups presentin said textile.
 2. The method of claim 1, optionally comprising anadditional post printing step of curing with melamine at a temperaturegreater than 180° C.
 3. The method of claim 2, wherein said bleedcontrol agent has a pH of between 2 and
 5. 4. The method of claim 3,wherein said textile is a synthetic material.
 5. The method of claim 4,wherein said cross-linking agent is an epoxide.
 6. The method of claim5, wherein said pretreatment solution farther comprises a surfactant. 7.The method of claim 6, wherein said pretreatment solution has aviscosity of less than 4 cPs.
 8. The method of claim 4, wherein saidcross-linking agent is an epoxide.
 9. The method of claim 9, whereinsaid pretreatment solution farther comprises a surfactant.
 10. Themethod of claim 10, wherein pretreatment solution has a viscosity ofless than 4 cPs.
 11. The method of claim 1, wherein said polymericbinder is a polyurethane.
 12. The method of claim 11, wherein said bleedcontrol agent has a pH of between 2 and
 5. 13. The method of claim 12,wherein said textile is a synthetic material.
 14. The method of claim13, wherein said cross-linking agent is an epoxide.
 15. The method ofclaim 14, wherein said pretreatment solution further comprises asurfactant.
 16. The method of claim 15, wherein said pretreatmentsolution has a viscosity of less than 4 cPs.
 17. The method of claim 13,wherein said cross-linking agent is a carbodiimide.
 18. The method ofclaim 17, wherein said pretreatment solution further comprises asurfactant.
 19. The method of claim 18, wherein said pretreatmentsolution has a viscosity of less than 4 cPs.